DE2422655A1 - DETERGENT COMPOSITION - Google Patents

Description

.-CHEM. WAITER AT J

alfredhoeppener

DR. JUR. DIPL-CHEM. RJ. WOIiP rg _Ma ; ^ ₇ ,

DIL JUR. HANS CHR. AX

MS FRANKFURTAMMAIN-MOGMSf 2422655

Our Mr. 19 286 -

The 'Procter & Gamble Company Cincinnati, Ohio, V.St.A.

-Detergent composition

It has long been known that "" aschaittal compositions are more effective in wdiches water than in Viasser, which contains significant amounts of dissolved "card" cations, such as calcium ion. Magnesium ion and the like. Contains. 7. ^R ash water has therefore been calibrated prior to use, usually by passing the water through columns of zeolite or other cation exchange materials. The use of such zeolite or other cation exchange materials for pretreatment of the water makes a separate container or apparatus necessary in which the water can slowly percolate through the ion exchange material to remove the undesired cations. Such pre-treatments for the purpose of compliance. make additional expenses for the user necessary, which result from the necessity of purchasing the Vi'eichaachapparates. .

Further means through which the tissue is optimal under conditions Washable in hard water include the use of water-soluble builder salts and / or chalates. Formers for the purpose of coraplexing the undesirable hardness, ^;. the cations and for the effective prevention of 7 / umbilical cord " with the fabrics and detergent materials in the Washing liquid. By using such water-soluble * However, builders are necessarily fed into the V / ater certain hangovers! Alien introduced into being incorrect treated wastewater can be undesirable. It exists

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ORIGINAL INSPECTED .. £ ■ '

hence a need for the creation of water softeners Builders in detergent composition without the requirement soluble builder additives.

Various methods have been proposed to exert builder and water softening effects simultaneously during the wash portion of a household laundry process without the need for water soluble detergent additives. One such process utilizes a phosphorylated wipe which can be added to the wash bath To bind hardness ions complex and which can be removed after each wash; see US-PS Kr. 3,4-24,54-5 ·

The use of certain clay materials for adsorption of hardness ions from washing liquids has also been proposed; see e.g. Rao, in Soap, Vol. 3, No. 3, Pages 3-13 (1950); Schwarz et al., "Surface Active Agents and Detergents", Vol. 2, pp. 297 et seq. (1966).

The zeolites, especially the naturally occurring ones Aluminosilicate zeolites have been proposed for use in detergent compositions; see US-ES Ur. 2,213,641 and also US-PS Mr. 2,264,103.

Various aluminosilicates have been proposed for use as additives to and for use with detergent compositions; see, for example, U.S. Patent No. 923,850; No. 1,419,625; and GB-PS ¹ η No. 339,355; No. 461,103; No. 462,591; and no. 522,097-

From the foregoing it can be seen that various methods have hitherto been used to cope with hardship from aqueous laundering systems during the laundering portion of a household laundering process. These methods however, have not been generally successful, primarily because of the inability of the materials described to

- 2 409848/103 ©

the free, polyvalent content of the aqueous washing liquid Effectively reduce metal ion to acceptable hardness values. Including in. 'Detergents together et really ignite To be useful, an ion exchange material must be sufficient Have cation exchange capacity to reduce the hardness of the V. 'ash bath without the requirement of excessive amounts of Significantly reduce ion exchangers. In addition, the ion exchange material must act quickly, i.e. it must Cation hardness in an aqueous wash bath to an acceptable level within the limited time (about 10 to 12 minutes), which is available during the washing section of a household washing process, to decrease. Optimally effective ion exchange materials should be able to reduce the calcium hardness to about 0.065 to 0.129 g / 3.8 l within the first .1 to 3 minutes of the washing section. After all, they are useful Cation exchange builders are desirable in substantially water-insoluble, inorganic materials which pose little or no ecological problems Waste water.

It has now been found that certain aluminosilicate materials both the high ion exchange capacity and have the rapid ion exchange rate required for cation exchangers Builder materials in detergent compositions required are.

Accordingly, it is an object of the present invention to provide detergent compositions that are insoluble contain inorganic aluminosilicate ion exchange materials.

Another object of the invention is to provide methods for To provide washing of fabrics in which the detergent compositions mentioned above are used will.

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The present invention is based in part on the discovery that cleaning and detergent compositions, those for the rapid reduction of the content of free, polyvalent Metal ion in washing liquid are now produced can be, if they use a special, water-insoluble aluminosilicate ion exchange material in combination with surface-active ingredients. In particular, the compositions according to the invention contain:

(a) about 5% by weight to about 95% by weight of a water-insoluble Aluminosilicate ion exchange material of the general formula

wherein ζ and y are integers of at least 6; the.-molvex ratio from ζ to y in the range from 1.0 to etv / a '0.5, preferably etv / a 0.8 to 1.0; and χ one integer from about 15 to about 264, preferably about 27i is; wherein the aluminosilicate ion exchange material a particle diameter of from about 0.1 microns to about 100 microns; a calcium ion exchange capacity of at least about 200 mg equivalents / g; and a Calcium ion exchange rate of at least etv / a 0.129 g / ', 8 l / min / g; and

(b) etv / a 5% by weight to about 95% by weight of a water-soluble, organic, surface-active agent from the anionic, nonionic, ampholytic and zv / itterionic surfactants and their terms Group.

According to a preferred embodiment of the invention has the water-insoluble aluminosilicate ion exchange material the formula

AlO ₂ . SiO ₂ ) ₂ . χ H ₂ O,

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wherein χ is an integer from about 20 to about 30, preferably from etv / a 27, means.

The yeast and detergent compositions according to of the invention contain in addition to the ion exchange material al and the organic detergent compound various others Ingredients commonly used in detergent compositions be applied. In particular, auxiliary water-soluble builders can be used in the compositions to support the removal of calcium hardness and to complexly bind magnesium cations in water, if dissolved magnesium salts create significant hardness problems.

In addition, the compositions according to the invention pH regulators' contain to adjust the pH to keep the washing liquid within a desired range. '.

The aluminosilicate ion exchange materials as used in the context of the invention can be prepared by a process particularly suitable for the formation of "detergent builders and water softeners" suitable materials. In particular, the aluminosilicates used here both have higher calcium ion exchange capacity as well as faster exchange rate than similar materials previously used as detergent builders have been proposed. Such a high rate of calcium ion exchange and capacity seems to be a function of several interrelated ones Factors resulting from the method of preparation of these aluminosilicate ion exchange materials.

An essential feature of the ion exchange builder materials used in the present ^{invention is that they are in the "sodium form 11. Es}

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'Surprisingly, it was found that, for example the potassium and hydrogen forms of the present Aluminosilicates neither show the exchange rate still have the exchange capacity that is necessary for optimal use as a builder.

A second essential feature of the ion exchange builder materials as used in the present invention "is that they are in the hydrated form, ie 10% to 28% by weight , preferably 10 % to 22 % by weight. -% _y contain water. Highly "preferred aluminosilicates contain about 18% by weight to about % by weight water in their crystal matrix. For example, it has been found that less strongly hydrated aluminosilicates, for example those with about 6 % V / However, ion exchange builders are not as effective when used in conjunction with a detergent composition. -

A third essential characteristic of the ion exchange builder materials, how they are used according to the invention is their particle size range. The corresponding Selection of small particle size particles results in rapid and highly effective builder materials.

The process given below for the preparation of the aluminosilicates takes into account all of the essential elements listed above. First, in the method, contamination of the Aluminosxlicatproduktes is avoided by various of sodium cations. For example, product washing steps involving acids or bases other than sodium hydroxide are avoided. Second, the process is designed so that the aluminosilicates are formed in their most hydrated form. Therefore, high temperature heating and drying are avoided. Third, takes place at

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Method of forming the aluminosilicate material in a finely divided state with a narrow range of small particle sizes. The need for such mechanical Zefkleinerungsstufen Of course, additional Mahlope- "configurations can be applied, reduce even further zn to the particle size. However, occurs to a much lesser extent in this method.

The aluminosilicates used according to the invention can obtained by the following procedure:

(a) Dissolution of sodium aluminate (Ka AlOp) in water to form a homogeneous solution, which preferably has a concentration of Na A10 _? of about 16.5% by weight;

C.

(b) Adding sodium hydroxide to the sodium aluminate solution of step (a), preferably at a weight ratio of NaOH: Na AlO ₂ = 1: 1.8, and maintaining the temperature of the solution at about 50 ° C until all of the KaOH is dissolved and a homogeneous solution is formed;

(c) Addition of sodium silicate (Na ₂ SiO, with a SiO ₂ to ΝβρΟ - weight ratio of 3.2: 1) to the solution of step (b) to form a solution with a weight ratio of Na ₂ SiO-S. : NaOH = 1.14: 1 and a weight ratio of Na ₂ SiO,: NaAlO ₂ = 0.63: 1;

(d). The mixture prepared according to step (c) is heated to about 90 ° C. to 100 ° C. and retained area for about 1 hour.

about 90 C to 100 C and maintaining this temperature

According to a preferred embodiment, the mixture of step (c) is to a temperature below about 25 ° C, preferably in the range from 17 ° C to 23 ⁰ C, cooled, and at this temperature for a period of about 25 hours to about 500 hours preferably about 75 hours to

etv / a 200 hours.

The mixture obtained from step (d) is cooled to a temperature of about 50 C and then filtered, to separate the desired aluminosilicate solids. If the low temperature ^ <25 ° C) crystallization method is applied, the precipitation takes place without additional preparatory steps filtered. If desired, the filter cake can be freed from excess base by washing (Deionized water is preferred to avoid cation contamination to avoid). The filter cake is reduced to a moisture content of 18% by weight to 22% by weight Dry using a temperature below about 150 ° C to avoid excessive dehydration. Preferred version will be drying is carried out at 100 ° 0-105 ° C.

The following is a typical preparation of the aluminosilicates as used in accordance with the invention in one Plant specified on a laboratory scale.

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Manufacture of aluminum triosilicate builder

Component: kg (lbs) kg (lbs)
(anhydrous) kg (lbs)
water Weight %
of the Ge
velvet: NaAlO ₂ - 25.974
(57.72) 22.254
(49,454) 3.722
(8.27) 16.40
(water
free) Sodium iIicate
(SiO ₂ : Na ₂ O =
- 3.2: 1) 37.134
(82.52) 13.925
(30,945)
■ ι 23.206
(51.57) 10.26
(water-
" free) NaOH 24.732 12.287 12,467 9.05 (54.96) (27,304) (27.66) (water
free) HpO (entioni 47.88 47.88 64.29 sated) (106.40) (106.40)

The sodium aluminate is dissolved in water with stirring and the sodium hydroxide is added. The temperature of the mixture is kept at 50 G and the sodium iicate is added with stirring. The temperature of the mixture is increased to 90 ° C to 100 ° C and held for 1 hour in this range with stirring to prevent the formation of Na ,. ₂ (AlO ₂ -SiO ₂ ) ^ ₂ . 27 H ₂ O to allow. The mixture is cooled to 50 ° C., filtered and the filter cake is washed twice with 45.4 kg of deionized water. The cake is dried at a temperature of 100 ° C to 105 ° C to a moisture content of 18 % to 22% by weight to obtain the aluminosilicate builder material. -

The aluminosilicates prepared in the above manner are characterized by a cubic crystal structure.

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Water-insoluble aluminosilicates with a MoTvernaXtnis of (AlO ₂ ): (SiO ₂ ) less than 1, ie-in the range between 1.0 and about 0.5, can "in" similar ¥; ^r else be prepared. These Aluniinosilication exchange materials. (AlOp: SiOp <1) are also capable of effectively reducing the content of free polyvalent hardness-forming metal ions in an aqueous washing liquid in a manner substantially similar to that of the aluminosilicate ion exchange material which, as described above, has a molar ratio

of AlO ₀ : SiO ₀ = 1. Examples of aluminosilicates, ti. , d. - ·

- Which have a molar ratio AlO ₂ : "SiO ₂ <1, and are suitable for use in the context of the compositions according to the invention, include;

Na ₈₆ A- (Al0 ₂ ) ₈₅ (Si0 ₂ ) ₁₀₆ _7-264H ₂ 0 and

Although fully hydrated aluminosilicate ion exchange materials are preferred within the scope of the invention, the partially dehydrated aluminosilicates of the general formula given above are also excellently suited for rapidly and effectively reducing water hardness during the washing process. In the process of making the instant aluminosilicate one from chmaterials, variations in reaction crystallization parameters can result in such partially hydrated materials. ¥ The above stated, aluminosilicates with about 6 % or less water content are not effectively applicable for the intended purpose in bagging. The suitability of the special, partially dehydrated, water-insoluble aluminosilicates for use in the compositions according to the invention can easily be determined and only requires routine experiments, such as those described here (calcium ion exchange capacity; exchange rate).

- 10 -

4098 * _{8/1030 or 1G} , nal, nspected

The ion exchange properties of the aluminosilicates used according to the invention can expediently be determined by means of a calcium ion electrode. In this method, the rate and capacity of Ca uptake from an aqueous solution containing a known amount of Ca ⁺⁺ ion are determined as a function of the amount of aluminosilicate xone exchange material added to the solution.

The water-insoluble, inorganic aluminosilicate ion exchange materials, which have been prepared in the above manner are by a particle diameter of about 0.1 microns to about loo microns marked * Preferred Ion exchange materials have a particle diameter from about 1 micron to about Io micron. More preferred water-insoluble aluminosilicates as used according to the invention are used are characterized by a particle diameter of about 0.2 microns to about 0.7 microns. Of the The term “particle diameter” means in the context of the present invention Invention the mean diameter of the particles of a given ion exchange material as defined by usual analytical methods are determined, such as microscopic determination, scanning electron microscope (SEM).

The aluminosilicate ion exchangers used in accordance with the invention are also characterized by their calcium oxide exchange capacity that characterizes at least about 2oo mg equivalent Calcium carbonate hardness / g of the aluminosilicate, calculated on an anhydrous basis, and which is generally generally Range from about 300 mg-equiv / g to about 352 mg-equiv / g lies.

The ion exchange materials as used according to the invention are, furthermore, through their exchanges of calcium speed, which is at least about o, 129 g /

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- 11 -

3.8 l / min / g of aluminosilicate (anhydrous) and in the range of about 0.129 g / min / g to about 0.389 g / l / min / g in terms of calcium ion hardness as used herein, the calcium ion exchange rate and the Water hardness, expressed by the number of grams that are equivalent to CaCo. Optimally, aluminosilicates for builder purposes have a Ca exchange rate of at least about 0.258 g / 3 _s 8 l / min / g.

- lla -

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The above procedure for producing the information from TiUSchinaterialicn can be modified as follows with regard to the different process stages. Step (a) can be modified by using solution concentrations of the NaAlO ₂ from 5 wt % to 22 wt%; the optimum concentration is 16% by weight to 16.5% by weight. Step (b) can be modified by destroying the KaOH. Sodium hydroxide is not required for the formation of the aluminosilicates used according to the invention, but its use is preferred to initiate the He action and to maintain the flow of action. Step (b) can be further modified using temperatures ranging from about 30 G to about 100 C; 50 C are preferred. Step (c) can be modified by varying the ratio of aluminate to silicate. In order to set the stoichiometric requirements of AlO ₂ : SiO ₂ = 1: 1 of a particularly preferred species in the end product, it is necessary in that special case to mix a molar ratio of AlOp: SiOp ("based on NaAlO ₂ and Na ₂ SiO- .) of at least 1: 1. In the latter case, it is highly preferred to use an excess of KaAlOp, since excess NaAlOp has been found to favor the rate and the course of the formation reaction of aluminosilicates have a molar ratio of AlO ₂ : SiO ₂ = 1: 1. Suitable water-insoluble aluminosilicate ion exchange materials which have a col ratio of AlO ₂ : SiO ₂ of less than "about 1.0, ie from 1.0 to about 0.5, can be prepared as described above, with the modification that the molar amount of SiO _{2 is} increased. The correct determination of the excess silicate to be used in the formation reaction can easily be used for optimization and requires only routine determinations.

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40984-8 / 1030

Stage (d) can be modified using temperatures from 50 ° G to 110 ° G "at temperature, 90 ° C to 100 ° C are optimal. Higher temperatures can be used if high pressure equipment is used to produce the aluminosilicates If the high temperature (90 to 10O ⁰ G) crystallization method is used, step (d) will normally require a formation reaction time of about 1 to 3 hours. d) in cooling the mixture of step (c) to a temperature below about 25 ° C., preferably in the range from 17 ° C to 23 ⁰ G _1, and the mixture at this temperature for a period of about 25 hours to 500 hours, preferably from about 75 hours to about 200 hours.

Following the formation of the aluminosilicates by the above procedure, the materials are recovered and dried. When used as ion exchange builders, the aluminosilicates must be in a highly hydrated form, ie contain 10% by weight to 28% by weight, preferably 10 % by weight to 22% by weight, v / water. Accordingly, the drying of the aluminosilicates must be carried out under controlled temperature conditions. Drying temperatures from about 90 ° C to about 175 ° G can be used. However, at drying temperatures of about 1-50 ° C to about 175 ° C, the less highly hydrated materials (about 10 % H ₂ Q) are obtained. Accordingly, it is preferred that the. To dry aluminosilicates at 100 ° C to 105 ° C, resulting in the optimal builder materials, which contain 18% to 22% by weight. At these last-mentioned temperatures, the stability of the preferred 27-hydrate form of the aluminosilicate is independent of the drying time.

The clay exchange materials described in the foregoing V / else can be used in washing liquids

4098 * 4 ^ / 1030

in Kennen von 8 0.005 wt "within about 1 to about 3 minutes. The concentration used will of course depend on the original map of the water and the wishes of the user. Highly preferred detergent compositions contain from about 20% to about 50% by weight of the aluminosilicate builder and from about 15 % to about 50% by weight of the water-soluble organic detergent compound. In another highly preferred embodiment, the compositions contain from about 10% to about 50% by weight of the aluminosilicate builder.

Detergent component.

The detergent compositions according to the present invention Invention can use all kinds of organic, water-soluble Contain Dstergensverbindungen as the aluminosilicate ion exchanger are compatible with all of these materials. A typical listing of the classes and representatives and .. Detergent compounds useful in the invention are found in U.S. Patent Kr.? 5,664,951 to which im Reference is made to this disclosure as part of the present invention. The following list of detergent compounds and mixtures included in the compositions of the invention are used for such materials representative, but not a limitation.

Water-soluble salts of the higher fatty acids, i.e. "soaps" , are as a detergent component of the invention Compositions useful. This class of detergents includes the common alkali metal soaps such as sodium, Potassium, ammonium and alkyl oil ammonium salts of the higher Fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms. May be-' fen know through direct saponification of fats and oils or

•. . - 14 -

409848/1030 bad original

dur-.ik Tieutralj.c-io.bion of free fatty acids produced v; er öci; . l'iesondors useful r.iml dio! Tatriuin and Kaliurasalze dov 'I- "ir? chuiii-en of fatty acids derived from coconut oil and TyIr: ie sodium or potassium tallow and coconut soaps.

Another class of detergents includes water-soluble salts, in particular the alkali metal, ammonium and alkylolamruonium salts, of the organic SchiefIsäurereakti- "onsprodukte, which have an alkyl group with about 8 to ο tv: a 22 carbon atoms and a sulfonic acid or sulfuric acid ester group in their molecular structure (The term "alkyl" is taken to mean the alkyl portion of the acyl groups.) Examples of this group of synthetic detergents which form part of the detergent compositions according to the present invention are the sodium and potassium alkyl sulfates, especially those which by sulfating the higher alcohols (Gg-G ^ p), formed by reducing the glycerides of tallow or coconut oil, the ITatriura and potassium alkylbenzenesulfonates, in which the alkyl group, about 9 to about 15 carbon atoms in a straight-chain or branched-chain arrangement contains, for example those from US ^{Pat. No. 1} η No. 2 "22o o99 and Kr. 2 4-77 38 5 are particularly valuable are linear, straight-chain alkylbenzenesulfonates, in which the alkyl groups have an average of about 13 carbon atoms, abbreviated as G ^ _v LAS.

Other anionic detergent compounds used in the framework ■ of the present invention are the potassium alkyl glyceryl ether sulfonates, in particular those ethers of higher alcohols which are derived from tallow and coconut oil. Sodium coconut oil fatty acid uionoglyceride sulfonates and sulfates; and sodium or potassium salts of alkylphenol ethylene oxide ether sulfate, which have about 1 to about 10 Athyleno: cide units each Contain molecule in which the Aükylpruppen about 8 to about 12 carbon to ffatome have.

- 15 - BAD ORIGINAL

409848/1030

Water-soluble, essential synthetic detergents are also part of the group as a part of the group moderate composition usable. Such nonionic detergent materials can generally be defined as compounds produced by condensation of alfcylene oxide groups (hydro- '. philer Katux *) with an 'organic hydrophobic compound which are aliphatic or alkyl aromatic can. The length of the polyoxyalkyl group associated with any special hydrophobeil group is condensed, can easily be adjusted so that a water-soluble compound is obtained which has the desired ratio-of hydrophilic and having hydrophobic elements.

For example, one known class of nonionic synthetic detergents is under the trade name "Pluronic" on the market. These connections are made through Condensation of ethylene oxide with a hydrophobic base is formed which by condensation of propylene oxide with propylene glycol arises. Other suitable nonionic synthetic Detergents include the polyethylene oxide condensates of alkyl phenols, a.B. the condensation products of alkyl phenols, the one alkyl group with about 6 to 12 carbon atoms in either straight or branched chain Have configuration, with ethylene oxide, the ethylene oxide being present in amounts which are 5 to 25 moles of ethylene oxide per mole Alkylphenol.

The water-soluble condensation products of the aliphatic Alcohols with 8 to 22 carbon atoms in either straight-chain or branched configuration with ethylene oxide, e.g. a coconut alcohol / ethylene oxide condensate with 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the Coconut alcohol fraction has 10 to 14 carbon atoms, are also nonionic detergents useful in the present invention.

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If

Its dipolar nonionic detergents include water-soluble / amine oxides, an alkyl radical having from about 10 to 23 carbon atoms and zv / ei Betrfco selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to etv: a group comprising 3 carbon atoms; water-soluble phosphine oxide detergents which contain an alkyl radical with about 10 to 28 carbon atoms and two radicals from the group comprising alkyl groups and hydroxyalkyl groups with about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents which "contain an alkyl radical having about 10 to 28 carbon atoms and a radical from the group consisting of alkyl and hydroxyalkyl radicals having 1 to 3 carbon atoms.

Ampholytic detergents include derivatives of aliphatic or aliphatic ^ derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical can be straight-chain or truncated and in which one of the aliphatic Substituents about 8 to 18 carbon atoms and at least an aliphatic substituent an anionic water-solubilizing agent Group contains.

Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in v / the aliphatic radicals are straight-chain or can be branched and wherein one of the aliphatic substituents has about 8 to 18 carbon atoms and one is one contains anionic v / water-solubilizing Gx-groups.

■ Other useful deterecens compounds for use In the context of the present invention, the water-soluble salts of the esters of a-sulfonated fatty acids include the etv / a 6 to 20 carbon atoms in the fatty acid group and etv / a contain 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids, the etv / a 2 to 9 carbon at oiae in the acyl group and about 9 contain up to about 23 carbon atoms in the alkane radical; Alkyl

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!.! ether sulfates containing from about 1 G to 20 carbon atoms in the AlkylpTupoe and about 1 to JQ oils contain ethylene oxide; water-soluble salts of olefin sulfonates containing about 12 to 24 carbon atoms; and β-alkyloxyalkanesulfonates which contain about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane radical.

Preferred water-soluble organic detergent compounds for use in the invention include linear alkyl benzene sulfonates having about 11 to 14 carbon atoms in the alkyl group; the alkyl sulfates having alkyl groups in the tallow range; the coconut alkyl glyceryl sulfonates; alkyl ether sulfates wherein the alkyl radical contains about 14 to 18 carbon atoms and 'wherein the average degree of ethoxylation varies between 1 and 6; the sulfated condensation products of Talp: alcohol with about J to 10 moles of ethylene oxide; olefin sulfonates, which contain about 14 to 16 carbon atoms; alkyldimethylaainoxides, in which the alkyl group has about 11 to 16 carbon atoms contains; alkyldimethylammoniopropanesulfonates and alkyldimethylammoniohydroxypropanesulfonates, in which the alkyl group in both types contains about 14 to 18 carbon atoms; soaps as defined above; the condensation products of tallow fatty alcohol with about 11 moles of ethylene oxide; and the condensation product it is secondary alcohol (C ^ on average) with 9 moles of ethylene oxide.

Particularly preferred detergents used in the invention include: sodium linear Cp-CQ alkyl benzene sulfonate; Triethanolamine C 1-4 ga-alkylbenzenesulfonate; Sodium tallow alkyl sulfate; Sodium coconut alkyl glyceryl ether sulfonate; the Natriumsalζ of a sulfated condensation product of a tallow alcohol with about J to about 10 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide;

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sulforiate; 3- (Ti, ci-Biinötliyl-K-kok
sulfohat; G-Cli-Dodocylbenz.yl-N _l Ii-diKethylaiumonio) -hexanoai ;; Dodecyldimethylamine oxide; Coconut alkylditaethylamine oxide; and the water soluble sodium and potassium salts of higher fatty acids containing 8 Ms 24 carbon atoms.

Any of the above detergents can be used alone or as appliances. Examples of. in the context of the "present invention" preferred detergent components are the following:

A particularly "preferred alkyl ether sulfate detergent component of the compositions according to the invention is a mixture of alkyl ether sulfates ,. where this mixture has an average (arithmetic mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of thoxylation from et '"a 1 to 4 moles of ethylene oxide, preferably se etv; a has 2 to 3 moles of ethylene oxide; see patent specification ρ 2 355 94o.2 (U.S. patent application Ser. No. 3o6 23o voia November 13, 1972).

In particular, such preferred mixtures include about 0.05 wt -. ° / _s to 5 Qevi .-% of mixtures of Cν, ρ ^ -ζ compounds, about 55 Ge ¹ A '.-% to 70 wt .-% of mixtures from C. ^ *, - compounds etv / a 25 wt .- ^ to 40 parts by fä mixtures of Cy _"i -_yjip-Verbinduneven and about 0.1 wt .- $ to ^5% Ge \ 't .- ° 'o of mixtures of C ^ g ^ Q compounds. Furthermore, such preferred Alkyläthersulfatmischungen contain about 15 Gev /.-% to 25 wt -.% Of mixtures of compounds having a Äthoxylierungagrad of O, about 50 to 65 Gev /.-% Ge \ -s ~ ^c / o of mixtures of compounds. with a degree of ethoxylation of 1 to 4, about 12% by weight to 22% by weight of mixtures of prebondun ^ on with an ethoxylation rate of 5 to 8 and

A0.9 8A8 / 1030

about 0.5 Gev!. ■■ -% to 10 Cev /.-% of mixtures of compounds with a degree of ethoxylation of more than 8.

Examples of alkyl ether sulfate mixtures included in the above The ranges given are given in Table 1.

"Table 1 .:

Mixture characteristics: Alkyl: Ether: Sulfate: Mixture: Medium carbon
chain length (number of
Carbon atoms) I.
14.86 II
14.68 III
14.86 . IV
14.88 12-13 C atoms (wt .- ^)
14-15 carbon atoms (wt .- #)
16-17 C atoms (wt. %)
18-19 C atoms (% by weight) 4th
55
36
5 1
65
33
1 1
65
33
1 3
57
38
2 Mean ethoxylation
grad (number of moles
Ethylene oxide) 1.98 2.25 2.25 3.0 0 moles of ethylene oxide
(Wt%)
1-4 moles of ethylene oxide
(Wt%)
5-8 moles of ethylene oxide
(Wt .- #)
9+ moles of ethylene oxide
. (Wt%) 15th
63
21
1 21
59
17th
3 22.9
65
12th
0.1 18th
55
22nd
5 salt K N / A • N / A N / A

Preferred "Olefinsulfonaf'-detergent mixtures which are useful in the present invention include olefin sulfonates containing from about 10 to about 24 carbon atoms. Such materials may be obtained by sulfonation of a-01efinen means unkomplexem sulfur dioxide and anschlies-

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send ITe u trau s at ion. under which conditions exist Suitono to the corresponding IJyöroxyalkansulfonaten hydrolyzed earth, manufactured wex ^ den. The alpha-olefin audio materials contain vorz-ugsv / iron "14 to 16 carbon · material atoms. These preferred oc-olefin sulfonate are in the US-PS Kr. 3,332,880 described, to which in the context of the present Invention is incorporated herein by reference.

Preferred α-olefin sulfonate mixtures consist essentially of about 30% by weight to 70% by weight of a component A, about 20 % by weight to about 70 % by weight of a component B and about 2% by weight. -% to about 15 Gev /.-? 5 of a component C, in which

(a) Component A is a system of double bond isomers of soluble salts of alkene-1-sulfonic acids with about 10 to about 24 carbon atoms, the mixture of positional isomers being about 10 % to about 25 % of an α , β-unsaturated isomer, etv / a 30% to etv / a 70 ° / o of a β, Τ-unsaturated isomer, from about 5% to about 25% of a y, cT-un £? esättigten Isoniers and about 5% to etv / a contains 10 % of a c ^ e unsaturated isomer;

(b) component B is a mixture of water-soluble salts of bifunctionally substituted sulfur-containing saturated aliphatic compounds with about 10 to about carbon atoms, the functional units being hydroxyl and sulfonate groups and the. Sulfonate groups are always present at the terminal frohlenstoffatom, while the hydroxyl group is bonded to a carbon atom which is at least 2 carbon atoms from the terminal carbon atoms and at least 90 ° / of Eydroxygeuppensubstitutionen in άοΐχ positions 3, 4 and 5 present o; and

(c) Component C is a mixture that is about. 30 %

- 21 -

. 409848/1030

JtS

. to 95 ° / o water soluble salts of Alkenaisulfonaten. with · about 10 "to about 24 carbon atoms and about. 5 % " to. represents about 70 % water-soluble salts of hydroxydisulfonates with about 10 to about 24 carbon atoms, whereby the alkene disulfonates have one sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an inner carbon atom which is not more than about 6 carbon atoms away from the terminal carbon atom , bound on iron, the alkene double bond between the terminal carbon atom and about the. 7 carbon atom, the hydroxydisulfonates are saturated aliphatic compounds with a sulfonate group bonded to a terminal carbon atom, a second sulfonate group bonded to an inner carbon atom that is not more than about 6 carbon atoms from the terminal carbon atom, and a hydroxyl group bonded to a Carbon atom is bonded that is no more than about 4 carbon atoms away from the point of attachment of the second sulfonate group.

Auxiliary builders.

As indicated above, the detergent compositions according to the invention in addition to the aluminosilicate ion exchange builders alternatively water-soluble builders, such as those for use in detergent compositions Are provided, included. Such auxiliary builders can be used to support the complex formation of hardness-forming Ions are used and are in particular in combination with the Aluniinosilicationenaustauschgorüstoffe in Situati- ■ onen valuable, in which magnesium ions in significant Extent contribute to water hardness. Such auxiliary builders can in concentrations of about 5 wt .- ^ to about 50 Gev.v #, preferably from about 10 wt. to etv-a 35 wt .- ^ S, the erfindunp-nreraäßeii '"aRchnimittelzuGauirriOnren are applied, to take advantage of their auxiliary fuel activity. Bie

• - 22 -. .

409848/1030

Auxiliary builders as described in the scope of the present invention; can be applied include any of the customary inorganic and organic water-soluble builder salts.

Such auxiliary builders can be, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxy sulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates. Specific examples of inorganic phosphate builders include sodium and ^{Kaliuintripolyphosphate:} pyrophosphates, phosphates and hexametaphosphates. The polyphosphonates include in particular, for example, the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-i-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorus builder nnectivity found in US Patent No. 3,159,531 η ^1. No. 3.21?, 030; No. 3,422,021; No. 3,4-22,137; No. 3, ^ 00,175; and No. 3,400,148, which are incorporated herein by reference as a disclosure. '

Phosphorus-free complexing agents can also be used as auxiliary builders in the context of the present invention be used.

Specific examples of phosphorus-free, inorganic auxiliary detergent builder ingredients include water soluble inorganic carbonate, bicarbonate and silicate salts. The alkali metal, e.g., sodium and potassium, carbonates, bicarbonates and silicates are particular within the scope of the invention useful.

Water-soluble organic auxiliary builders are included of the invention is also useful. For example, the alkali metal, ammonium and substituted ammonium

- 23 409848/1030

polyacetates, -carboxy] ates, -polycarboxylates and -polyhydroxysulphoxates useful auxiliary builders in those according to the invention S'usaniniensGtsungen - Special Examples of Polyacetate and polycarboxylate builder salts include sodium, Potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, Mellitic acid, eenzene polycarbonic acid and citric acid. .

Highly preferred phosphorus-free auxiliary builder materials include sodium carbonate, sodium bicarbonate, sodium silicate, Sodium Citrate, Sodium Oxydisuccinate, Sodium Me Hi that, sodium nitrilotriacetate and sodium ethylenediainetetraacetate as well as their mixtures.

Other highly preferred auxiliary builders are the ^ folycarboxylate builders disclosed in U.S. Patent No. 3,308,067 and to which reference is made as a disclosure within the scope of the present invention. Examples of such Materials include the water soluble salts of Homo- and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, Citraconic acid, methylenemalonic acid, 1,1,2,2-ethane tetracarboxylic acid, Dihydroxy tartaric acid and ketomalonic acid i

Further preferred auxiliary builders for use in the context of the present invention include those which are water-soluble Salts, especially the sodium and potassium salts, of Carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis -cyclopentane tetracarboxylate and hiIorglucintrisulfonat.

Specific examples of highly preferred phosphorus-containing ones Auxiliary builder salts for use in Scope of the present invention include. Alkali pyrophosphates, y; obei is the weight ratio of ion exchange.

- 24 -

409848/1030

material to pyro phosphate is in the range from about 1: 2 "to about 2: 1. Further preferred auxiliary co-builders, xixs sodium tripolyphosphate and the alkali salts of nitrilotriacetic acid, also give superior performance with a weight ratio of ion exchange material to auxiliary builder salt in the range of about 1 : 1. to about 1: 3. The ion exchange aluminosilicates in combination with citrate auxiliary builder salts result in a superior removal of free metal ions in washing liquids if the zeolites used have a molar ratio of AlOo: SiO ₂ = 1: 1. The above preferred ranges of auxiliary builder to The aluminosilicate of the builder components can be represented by mixtures of these builders.

The detergent compositions according to the invention, which contain the aluminosilicate ion exchange builders and the water-soluble auxiliary builders are therefore valuable because the aluminosilicate preferentially adsorbs calcium ions in the presence of the auxiliary builder material. Accordingly, the hardness-forming calciucions become in the first place Line removed from solution by the aluminosilicate while the auxiliary builders for the complex binding of other polyvalent hardness-forming ions, such as magnesium and iron ions, remain available.

The detergent compositions according to the invention may contain all kinds of additional materials that are commonly used in laundry detergent and cleaning agent compositions being found. For example, such compositions can contain thickeners and soil suspending agents such as Carboxymethyl cellulose and the like. Enzymes, especially the proteolytic and lipolytic enzymes such as them commonly used in detergent-containing detergent compositions can also be present therein. Various perfumes, optical bleaches, fillers, that Anti-caking agents, fabric softeners, and the like.

- 25 - '409848/1030

may be present in the compositions he findungc contemporary ¹ · to get um.die usual benefits that such result gen li & ter ialien in Waschmittelzusaiamensetzun- 'through use. Other such additional materials can be used in the context of the invention provided that they are compatible and stable therewith in the presence of the Aluiainosilicationenaustauschgerüststof. ■ ·.

! The granular washing middle compositions according to the invention may advantageously also comprise one-Peroxybleichkomponente in an amount of about 3 Gevi .-% to about 40 wt -.% _Y preferably from etv / a 8 wt -.% To about 33 Gev /.-# , contain. Examples of suitable peroxy bleach components for use in the invention include perborates, persulfates, persilicates, perphosphates, percarbonates and, more generally, any inorganic and organic peroxy bleaching agents known to be useful in detergent compositions.

The detergent compositions according to the invention can by any of several known procedures for the production of commercial detergent compositions produced v / earth. For example, the compositions can be prepared by simply admixing the aluminosilicate ion exchange material to the water-soluble organic detergent compound. The auxiliary framework material and any additives used can, if desired, simply be mixed in. Alternatively can be an aqueous slurry of the aluminosilicate ion exchange builder, what dissolved water-soluble organic detergent compounds and those optionally used as well as auxiliary materials. contains, spray-dried in a tower to obtain the granular composition. The granules of such spray dried detergent compositions contain the aluminosilicate ion exchange builder, the organic detergent compound and the optionally used

- 26 409848/1030

IS

and auxiliary materials.

. Alternatively, the aluminosilicate ion exchange materials used according to the invention can be used separately in aqueous Y / ash and / or rinsing baths in order to reduce the hardness-forming cations. When used in this manner, the user can simply mix an effective amount, ie, an amount sufficient to reduce the hardness to about 0.065g to 0.129g / 3.8L, into the aqueous bath, followed by a add commercially available detergent composition of his choice. When used in this manner, the aluminosilicate is generally added in an amount of from about 0.005 % to about 0.25% by weight of the aqueous bath.

According to the invention, the ion exchange aluminosilicates can also be used in combination with standard cationic fabric softeners when rinsing fabrics. In this application, the aluminosilicates remove the hardening cations and lead to a softer handle on the plasticized material. typical cationic fabric softeners useful in combination with the aluminosilicate ion exchangers include tallow trimethyl ammonium bromide, tallow trimethyl ammonium chloride, ditallow dimethyl ammonium bromide and ditallow dimethyl ammonium chloride. V / ässerige fabric softening compositions that contain the Aluminosilicationenaustauscher, have a content of about 5 wt .-% to about 95 wt .- ^ of the aluminosilicate and about 1 wt -.% To etv / a 35 wt .-% of the cationic fabric softener.

The detergent compositions according to the invention are used in aqueous fluids to clean surfaces, particularly fabric surfaces, using any of the standard washing and cleaning methods will. For example, the compositions according to the invention are particularly suitable for use in automatic standard

- 27 409848/1030

washing machines "at concentrations of about 0.01 wt% to about 0.50 wt Qqw. ~% . As is the case with most commercially available detergent-containing detergent compositions, the dry compositions according to the invention are usually an ordinary aqueous washing solution in an amount of about 1.0 cup / about 65 liters ( 17 gallons) of wash water-added.

Although the aluminosilicate ion exchange builder materials as used in the present invention effect the removal of calcium hardness ions within a wide pH range, it is preferred that agent compositions containing such materials have a pH in the range of about 8.0 to about 11, preferably about 9.5 to about 10.2. As is the case with other standard detergent compositions, the compositions exert their action optimally within the basic pH range for removing dirt, triglyceride dirt and stains. Although the aluminosilicates used according to the invention in themselves result in a basic solution, the detergent compositions which contain the aluminosilicate and the organic detergent compound can additionally contain about 5% by weight to about 25% by weight of a pH-adjusting agent. Such compositions can also contain the adjuvant materials and optional ingredients as described above. The pH adjusting agent which is used in such compositions is selected such that the pH of a 0.05 wt .- ^ aqueous mixture of the composition in the range of about 9> 5 bi ^s is about 10.2 .

The pH value to be used if necessary

■ '"- 28 -

4.0 9848/1030

Agents useful in the tapping of the invention include any of the vapor soluble basic materials commonly employed in chemical compositions. Tropical examples of such water-soluble materials include the sodium phosphates; Sodium silicates,
in particular those which have silicon dioxide: sodium oxide-Ge '". ratios from about 1: 1 to about 1: 3.2, preferably from about 1: 1.7 to about 1: 2.3; sodium hydroxide Potassium hydroxide, triethanolamine, diethanolamine, ammonium hydroxide, and the like. Preferred pH control agents include sodium hydroxide, triethanolamine and sodium silicate.

The following examples are typical of the invention Detergent compositions, however, are not limiting of the invention.

Example 1: It is a spray dried laundry detergent made up of the following composition having:

Component:

Surface active system, containing:

Sodium tallow alkyl sulfate

Condensation product from 1 mole of a sec. dear fatty alcohol with about 15 carbon atoms and about 9 moles of ethylene oxide

Calo _{2 2} SiO _{2) 12} .27 V / ater

Weight ratio of anionic to nonionic components = 4-, 5: 1

Weight %

22nd

Manufactured in the manner described above;
mean particle diameter: 5 microns.

- 29 409848/1030

The above composition results in an excellent quality, under normal household conditions, in a liquid with a hardness of 0.4-55 F / 3 S 1 a concentration of the composition; in the washing liquid of about 0.12% by weight. Under such conditions, the foaming and cleaning performance of the composition of Example 1 is found to be favorable compared to conventional high-foaming anionic detergent formulations which contain full builders. Such a composition is pourable and is produced with conventional spray drying equipment.

Compositions with essentially the same performance characteristics are obtained when in the composition of Example 1 described above, the sodium tallow alkyl sulfate by an equivalent amount of potassium tallow alkyl sulfate, sodium coconut alkyl sulfate, Potassium coconut alkyl sulfate, sodium decylbenzenesulfonate, Katriumundecylbenzenesulfonat, Eatriumtridecylbenzenesulfoiiat, disodium tetradecylbenzenesulfonate, sodium tetrapropylenebenzenesulfonate, Potassium decylbenzenesulfonate, potassium undecylbenzenesulfonate, potassium tridecylbenzenesulfonate, Potassium tetradecylbenzenesulfonate or potassium tetrapropylene benzoε Ulfonat is replaced.

Compositions having substantially the same quality, essentially the same physical characteristics features and wesentliehen same ¹ processability are obtained when in the above-described composition of Example Λ is the condensation product from the secondary alcohol having 15 carbon atoms and 9 moles of ethylene oxide by eine.äquivalente amount of the condensation product of tridecyl alcohol with about 6 moles of ethylene oxide (HLB = 11.4-); the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide (HLB = 12.0); Neodol 23-6 _T 5 (HLB = 12); Neodol 25-9 (HLB = 13.1); or Tergitol 15-S-9 (HL3 = 13.3) is replaced.

- 30 409 8 4 8/1030

example

It becomes a spray dried one

raittelzusaramensetzuiiP: manufactured in sov / ohl Ca ⁺⁺ - as

also Mg ⁺⁺ ~ hardness on v / icing water · can be used; it has the following composition:

Component:

Surface active system, containing:

Sodium linear alkyl benzene sulfonate, wherein the alkyl group has an average length • Has about 11.8 carbon atoms

Condensation product from 1 mole of coconut fatty alcohol and about 6 moles of ethylene oxide

₁₂ (AlO ₂ .SiO ₂ ) ^ ₂ .27 H ₃ O

Sodium silicate (Na ^ / SiCU weight ratio: 1 _: 2.4)

Sodium citrate

Sodium acetate

Sodium toluene sulfonate

water

Minor components

4.7 %

Ge v /. Ratio
anionic
to non-ionic
Components =
4.26: 1

24.7

25.0

15.0

20.0

5.0

2.0

rest

* Manufactured in the manner described above;
mean particle diameter: 7.5 microns.

The composition of Example 2 provides excellent fabric ^{cleaning performance when, under normal household laundry conditions, a washing liquid with mixed Ca ++} and Mg ⁺⁺ hardness of 0.455 g / 3.8 1 at a concentration of the composition in the washing liquid of about 0, 12 % by volume is applied. The pH of the composition

- 31 409848/1030

Ji

dies.er solution is about 10.2. Under such conditions the switching capacity of the composition of Example 2 proves to be favorable in comparison with that of conventional, high-foaming anionic detergent formulations containing full builders. Such a composition is easy pourable and stable in storage; it is done with the usual spray drying device manufactured .

Compositions with essentially the same quality of performance, essentially the same physical characteristics and substantially equal processability are obtained when in the above composition the sodium citrate through an equivalent amount of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxydisuccinate, Sodium mellitate, sodium nitrilotriacetate, sodium ethylenediamine tetraacetate, Sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconate, Sodium polycitraconate, sodium polymethylene malonate or their mixtures is replaced.

A composition with essentially the same quality of performance, essentially the same physical characteristics and substantially the same processability is obtained when included in the composition of Example 2 above about 3% by weight sodium perborate solids are incorporated while all other components are essentially the same Maintain relative proportions. Such perborate compositions are particularly suitable for use under the Suitable washing conditions that are usually used in Europe Find.

If the entire system of surface-active constituents in the above composition is replaced by an equivalent amount of the alkyl ether sulfate mixtures I, II, III or IV, as appear in Table Λ , then an excellent detergent performance is obtained.

409848/1030

In the above composition, the ^ ₂ (AlQ ₂ .SiO ₂ ) ^. 27 H ₂ O through
Ka ₁₂ (AlO ₂ .SiO ₂ ) ^ ₁ p.20 Pi ₂ O or Ha ₁₂ C Al ₃ . SiO ₂ ) ^ .30. H ₃ O · replaced, equivalent results are obtained.

Example 3: A phosphorus free detergent composition is made from the following components:

Component: · Gew.-ff;

* Surface active system 35

Triethanolamine (pH adjustment agent) 7

NaOH (agent for pH adjustment) - 0.5 ** Ka _i2 (A10 ₂ .Si0 ₂ ) _i2 .27 H ₃ O 35

Sodium citrate 15

V / ater and minor ingredients rest

The surface-active system contains an α-olefin sulfonate mixture which consists essentially of about 30% by weight to about 70% by weight of a component A, about 20% by weight to about 70% by weight of a component B. and etv / a consists of 2% to about 15 % of a component C, wherein

(A) component A is a mixture of double bond position isomers of water-soluble salts of alkene-1-sulfonic acids, containing about 10 to about 24 carbon atoms, the mixture of positional isomers etv / a 10 % to about 25% of an a _t ß-unsaturated isomer, etv / a 30% to about 70% of a ß,] T-unsaturated isomer, from about 5% etv his / a 25% of a ^^ - containing unsaturated isomer and about 5% about 10% of his cf ₇ e-unsaturated Isoniers;

(b) component B is a mixture of water-soluble

- salts of bifunctionally substituted, sulfur-containing, saturated aliphatic compounds with about 10 to about 24 carbon atoms, the functional

j: 33 _

409848/1030

IS

Normal units represent hydroxyl and sulfonate groups and the sulfonate group is always present on the terminal carbon atom, while the hydroxyl group is bonded to a carbon atom which is at least 2 carbon atoms away from the terminal carbon atoms, and at least 90 % of the hydroxyl group substitutions in 3, 4 and 5 - positions exist; and

(c) component C is a mixture of about 30% to 95% of water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms and about 5% his about 70 ° / o water soluble Salzenvon Hydroxydisulfonaten with about 10 to about 24 carbon atoms, wherein the alkene disulfonates a sulfonate group bonded to a terminal carbon atom and a second sulfonate group bonded to an inner carbon atom which is not more than about 6 carbon atoms away from the terminal carbon atom, the alkene double bond is distributed between the terminal carbon atom and approximately the 7th carbon atom, the hydroxydisulfonates are saturated aliphatic compounds having a sulfonate group bonded to a terminal carbon atom, a second sulfonate group bonded to an inner carbon atom that is no more than about 6 carbon atoms from the terminal carbon atom - and a hydroxyl group which is bonded to one more than sth a carbon atom located 4 carbon atoms away from the binding site of the second sulfonate group is present.

** Manufactured as described above.

Average particle diameter: 12 microns.

The composition of Example 3 to an aqueous bath of 43 ° C in an amount of 0.15 wt -% added.

St.

and for y / ash oily govob · ;? used. It will be excellent Purifications erp; 3bnise-e took place under conditions in which the initial water hardness is 0.12 g / 1 to 0.205 g / l (7 to 12 grains / gallon) mixed hardness.

If, in the composition given above, the surface-active system is replaced by an equivalent amount of sodium-linear-C 1 -C 4 -alkylbenzenesulfonate; ITsodium tallow alkyl sulfate; Sodium coconut alkyl glyc. Eryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 5 to about 10 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide; 3- (N, IS ^T -dimethyl-K'-coconut alkylammonio) -2-hydroxypropane-1-sulfonate; 5- (1T ₁ N-dimethyl-N-coconut alkylamnionio) propane-1-sulfonate; 6- (N-dodecylbenzyl-N, N-dimethylammonio_) hexanoate; Dodecyl dimethyl amine oxide; Replaced coconut alkyldimethylamine oxide and the water-soluble sodium and potassium salts of higher fatty acids with 8-24 carbon atoms or their mixtures, thus ensuring equivalent results.

If, in the above composition, the surface-active system is replaced by an equivalent amount of a mixture of alkyl ether sulfa compounds which contains about 0.05% by weight of 4 to 5% by weight of a mixture of C ^ p ^^ compounds; about 55 Gev.-.- ° / o to 70 Gevr .-% of a mixture of C ^ _.-- compounds; about 25 wt .-% to 40 wt .- ^ of a mixture of ^ _Λ α _Λ η ~ compounds; etv / a 0.1% by weight to 5% by weight of a mixture of C.Q_ ^ q compounds; etv; a 15 weight -% to 25 Gev; .-% of a mixture of compounds having a Athoxylierungsgrad Oj of about 50 Gev.. .-% to 65 wt -% of a mixture of compounds having a degree of ethoxylation of 1 to 4; about 12% by weight to 22% by weight of a mixture of compounds with a degree of ethoxylation of 5 to 8; and about 0.5 weight -% to 10 Ge '^ -% of a mixture of compounds having a Äthoxylierungsp. rad of more than 8 replaced, are equivalent results

4,984 ³ ! / Ίθ3Ο

Si

s i rather ge s t'G lit.

Is in the composition given above the sodium citrate by an equivalent amount of sodium carbonate, sodium bicarbonate, __ sodium ilicate, sodium oxydisuccinate, Sodium mellitate, sodium nitrilotriacetate and the polymers Carboxylates as described in US-FS No. 5,508,067 are, or their. Replacing mixtures, an effective detergent action in hard water is ensured.

Used in the above composition is the sodium citrate successively by an equivalent amount of the sodium and potassium salts of carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentante tracarboxylät or Phloroglucintrisulfonat replaced, so an effective detergent action is ensured in hard water.

Example 4: A soap-based detergent granulate is produced from the following components:

Component: weight -%.

Sodium Soap ^ ¹ ^ 42.6

Potassium Soap ^ " 11.2

C2>

10.7

8.8

Sodium silicate 8.9

Sodium citrate 11.9

Brightener 0.57

Perfume ' 0.17

Water 3.4

Miscellaneous Eest

(1) = soap endmix containing 90 % daily and 10 % coconut soaps;

-36 409848/1 030

(2) = Satrluasalt of 'athoxylated'! Tallow alkyl sulfate

Eic on average; about 3 units of ethylene oxide per molecule;

(3) = sodium al ζ of linear alkylbenzenesulfonate with

an average alkyl chain length of about 12 carbon atoms.

75 parts by weight of the soap-based grains prepared as indicated above are mixed with 25 parts by weight Na ^ ₂ (AlO ₂ -SiO ₂ ) ^ ₂ · ² 7 ^H 2 ° ( ^ner S ^es " ^{tellt iEL otsn the} manner indicated;. particle size 25 microns) are mixed, the composition is applied in an amount of 0.12 wt .-% of the Y / asehflüssigkeit and gives excellent fabric cleaning and foaming characteristics in water Aiit a hardness of 0.171 g / l (10 grain /Gallon).

The composition of Example 4- is made by adding modified by 3 parts by weight ITatriuiaperborat, with excellent Hot water (4 9 - 82 G) cleaning properties. be ensured.

As can be seen from the foregoing, the aluminosilicate ion exchange builder materials can be added to any type of detergent composition. In addition, the aluminosilicate builders in combination with water-soluble builders that complexly bind magnesium, iron and other polyvalent water-hardness-forming cations can also be used in combination with any type of detergent composition. Depending on the usage habits of the user, it is useful to add the aluminosilicate builder or aluminosilicate plus builder material to an ash or rinse liquid separately from the detergent composition. 3ine such separate use allows for flexibility in the V.'ahl of the detergent composition that is applied by the user, while at the same desired advantages of the oils according to the ER- Gerüststoffniaterialien

- 37 409848/1030

• findun £ can be obtained. The separate use of the aluminosilicate builders and aluminosilicate plus auxiliary builder compositions for softening water represents an embodiment of the present invention.

Since most hard waters contain polyvalent metal ions in addition to calcium ions, the use of the aluminosilicate builders as plasticizers of the water is preferably carried out in the presence of an auxiliary builder of the type described above. Such auxiliary builders can be any of the phosphorus-containing builders or, in areas where such builders are not permitted, any of the phosphorus-free builder materials described above. The aluminosilicate builders and the auxiliary builders can of course be added separately to the water in order to exercise their plasticizer function. However, it is more expedient to add such materials to the water to be treated at the same time. Accordingly, compositions are provided to the user containing from about 5% to about 95% by weight of the aluminosilicate builder materials and from about 5% to about 95 % by weight of an auxiliary builder of the type described above. Preferably such compositions will be a Ge7. ^r T ratio of aluminosilicate: "1 to about 1: 5 have Such compositions can the user be provided in any of the physical forms available which aschinittelgerüststoffe for use as ^ 'are useful, such as dry powders, auxiliary builder of from about. 5 Tablets, pre-measured packets, or in water-soluble packs which are simply added to the softening solution. Various adjunct materials such as bleaches, blueing agents, fabric softeners, foam control agents, perfumes, sanitary ware and the like can be incorporated into such compositions if desired. to get the additional benefits desired.

AO9848 / 1030

The in. High would let desired speed and. Ioneriaustauschkapazität the Aluuiinosilicatraaterialien, ν ie? They are used erfiridungsgeiaäß, it is clear v / Enii such materials "used to Vorweichmachen of washing liquids v / ground. To be suitable for such use, the materials must not be so slow in operation that they require excessive waiting periods before adding a laundry detergent composition to the wash liquor. Also, it is equally undesirable to dated. To require users to use materials of such low ion exchange ability that an undesirably large amount is required to effectively complex hardness ions. For these reasons, the aluminosilicates according to the invention are particularly suitable for such builder and water repairs purposes.

Below is an example of a builder composition indicated according to the invention, which is suitable for use in water, which is any polyvalent hardness-forming Contains cations.

Example 5:

Component: wt. -% _;

₁₂ (AlO ₂ -SiO ₂ ) ₁₂ .27 H ₂ O 50 Sodium citrate 50

* = Manufactured as described above. Particle diameter: 100 microns.

The above composition is used as a granular powder Provided- The powder is added in an amount of 56.7 g / 76 liters (2 ounces / 20 gallons) of the water and stir for 1/2 minute. During this time, the hardness cations essentially ground to a Y / er of about 0.017 to 0.034 g / l (1 to 2 grain / gallon) (based on V / water with a hardness of 0.12 g / l; 7 grain / gallon). Then will

- 39 409848/1030

a commercially available; V.'as chmit t elae tor pens mixture of the v: ü :: se-ricen Bad added. Fabrics washed in such pre-softened water become more effective purified than in water that has not previously been plasticized.

_{If the (AlO 2} .SiOp) ₁ 0-27 H ₃ O in the above composition is replaced by an equivalent amount of ₁₂ (AlO ₂ .SiO ₂ ) ₁₂ .20 H ₂ O or Na ₁₂ CAl ₂ -SiO ₂ ) ^ ₂ .30 H ₃ O, prepared as described above, replaced, equivalent results are obtained.

Used in the above composition is the sodium citrate by an equivalent amount of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxydisuccinate, Sodium mellitate, sodium nitrilotriacetate, Sodium Ethyl Ethyl Tetraacetate, Sodium Polymaleate, Sodium Polyitaconate, Sodium polymesaconate, sodium polyfumarate, sodium polyaconitate, Sodium polycitraconate, sodium polymethylene mal onate, sodium carboxymethyloxymalonate, sodium carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclohexane tetracarboxylate, Phloroglucintrisulfonat or their mixtures replaced, so an effective cleaning in hard Water secured.

The above compositions are applied and made in concentrations of 0.005% by weight to 0.25% by weight Water containing polyvalent cations is effectively softened.

The aluminosilicate builders and aluminosilicate plus auxiliary builder mixtures, as described herein are useful in any type of cleaning composition. They can also be effective in detergent-containing floor cleaning agents, Abrasives and the like can be used in which water also presents detergent problems. Typical abrasive

4-0 9848/1030

agents can be, for example, about 25% by weight to about 95 % by weight of an abrasive (eg silica), about 10 % by weight to about 35% by weight of an aluminum inosilicate builder of the type described above, about 0% wt .- ^ to about 20 Gev;.. .-% of an auxiliary builder, as described above, and about 0.2 Gevi ~% to about 10 wt -% ■ an organic Deterge ns compound.

Example 6: A detergent base granulate with the The following composition is made by conventional spray drying manufactured:

Components: parts by weight;

TAE ₃ S. ^ ¹ ^ 14.5

Sodium tallow alkyl sulfate 2.5

Silicate solids

(Ratio Na ₂ O: SiO ₂ = 2.0) 13.0 "

Sodium sulfate 15.0

Minor ingredients including "borrowed ITatriusitoluolsulfonat, trisodium sulfosuccinate, Humidity, etc. 5.0

(1) = sodium salt of ethoxylated tallow alkyl sulfate with on average about 3 ethylene oxide units per molecule.

A mixture is then prepared comprising the above detergent base granules and a builder component such as it is stated below in the stated proportions. The composition thus obtained is used for cleaning of polyester rags used with a clay Dirt composition have been stained. To this Purpose v / ground the cloths for 10 minutes at 40 C in a ·

Washed washing liquid, the 0.12 wt -.% Of the above-YTaschmittelzusarp inensetzung contains. The hardness and the calcium / magnesium ratio are varied as indicated. After this

409848/1030

2A22655

Y; asclien are, the rags, pult, ous removed from the Y / ash machine and then dried. The cleaning performance is the sum of the Kunter-V.'eichF \ raäbev. ^r validate with a · hardness of 0; -0.034; -0.058; 0.10; 0.1 ?; 0.17 and 0.20 g / l (0, 2, 4, 6, 8, 10 and 12 grains / gallon) expressed (Ca / Mg = 2/1), the Hunter whiteness being equal to O, if 0.06% by weight of sodium sulfate are used instead of the builder mixture, and 100 corresponds to if 0.05% by weight of sodium tripolyphosphate is used as the builder component. The substitute values of 0.06% correspond to the amount of the components in the washing liquid.

The builder component is a mixture of one Aluminosilicate of the formula

.SiO ₂ ) ₁₂ .27

made as indicated above and having an average particle diameter of 3 microns has, and a Hilxsgerüsts from the sodium pyrophosphate, Sodium tripolyphosphate, ITatriuninitrilotriacetate and Fatriuiacitrate group.

The basic detergent granulate represents 0.06-Gev /. -% of the ash liquid; the remaining 0.06% by weight is a builder component of the type indicated. The degree of ice results were as follows.

Aluminosilicates Sodium pyr 0, .%
phosphate: ^ ' Hunter
Degree of coldness :. 0.02
0.03
0.04 0.04
0.03
0.02 117
102
94

(1) = in Gev; .-% of the washing liquid

- 42 409848/1030

Sodium citrate is evaluated as an auxiliary rust substance in place of Iiatriuiup2.rr-ophosp} iate, whereby the stated test conditions are observed. In addition, the Ca / Mg Härtev ^"r erte be varied in the manner indicated. The Hunter whiteness values were as follows:

Ca: Mg "> ^ 1 {1)
Aluminosilicates ^J. Natr IUIa ₇ -. ·. Hunter citrate: ^ ^u Whiteness: 1 : 1 0.04 0.02 55 • 0.05 0.05 61 0.02 0.04 51 2: 1 0.04 . 0.02 58 0.05 0.05 52 0.02 0.04 55 5 '. 0.04 0.02 57 0.05 O ₁ O? 54 0.02 0.04 50

(1) = in% by weight of the washing liquid.

The sodium salt of nitrilotriacetic acid and sodium tripolyphosphate are also rated as auxiliary builders replacing the sodium pyrophosphate builder, the test conditions given above are observed. The calcium: magnesium ratio is 2: 1. the Hunter grades are as follows:

- 45 -409848/1030

ff

LlumxTio-, .χ
silicates ^; Sodium-
nitrile »- ^ n
triacetate - I'T & trium-
tripoly ,,,
pliosphate: ^ ^J 0.04. Hunter
v / degree of ice: 0.02 0.04 0.03 108 0.03 '0.03 0.02 82 0.04 0.02 • 64 0.02 95 0.03 91. 0.04 79

(1) = in% by weight of the extinguishing liquid.

The above test results illustrate the superior cleaning performance exhibited by the use of special combinations of aluminosilicates and auxiliary builder salts in connection with detergents.

Compositions capable of giving substantially equal performance are obtained when the Na · ^ trium salt of ethoxylated tallow alkyl sulfate with an essentially equivalent amount of sodium tallow alkyl sulfate, Sodium coconut alkyl sulfate and sodium decylben2sol sulfonate is replaced.

Essentially the same results are also obtained when the Na " _o (A10 ~ .SiO ₀ ) ^ ₀ .27 H ₀ O is replaced by an equivalent amount of Na ₁₂ (AlO _2. SiOO ₁₂ .20 H ₂ O;

Na ₁₂ (AlO ₂ .SiO ₂ ) ₁₂ .30 H ₂ O; iTa ₈₆ / "(Al0 ₂ ) _a6 (Si0 ₂ ) ₁₀₆ J7.264 H ₂ O; or Na ₆ / ~ (Al0 ₂ ) ₆ (Si0 ₂ ) ₁₀ _7.15 H ₂ O is replaced.

Example 7: It becomes a granular detergent composition manufactured, which contains the following components:

- 44 409848/1030

Vi

Stock text: G-ew. -Parts: TAE ₃ S ^ 14.4 Sodium tallow alkyl sulfate 2.1 Sodium tripolyphosphate 24.0 Na ₁₂ (AlO ₂ .SiO ₂ ) _i2 · 27 H ₃ O ^ ■) 18.0 Sodium sulfate 36.6 Brightener 0.9 ! "luminosity 5.0

(1) = sodium salt of ethoxylated tallow alkyl sulfate with im

Average about J> ethylene oxide units per molecule.

(2) = Manufactured as described above. Mean particle diameter: 3 to 5 microns.

The above composition is capable of excellent soil removal and cleaning performance in usual Washing to result if water with a high initial water hardness, for example from 0.12 to 0.24 g / l (? To 14 grain / gallon) Calcium / magnesium hardness.

- 45 409848/1030

Claims (1)

1. Laundry detergent preparation leading to rapid reduction. · '. ., the content of free, polyvalent metal ion in a aqueous solution is capable of containing: ■ (a) about 5% by weight to about 95% by weight of a water-insoluble Aluminosilicate exchange material of general. Formula, Na _z r <A10 ₂ ) _z . - (SiO ₂ ) _y J _x H ₂ 0, · where ζ and y are integers of at least 6 * the molar ratio of ζ to y is in the range from l, o to about o _a 5 and χ is an integer from about 15 to about 26k, wherein the aluminosilicon ion exchange material has a particle diameter of about 0.1 microns to about 100 microns, a calcium ion exchange capacity of at least about 200 mg equivalent / g, a calcium ion exchange rate. has a duration of at least about ο, 129 g / 3.8 1 / min / g and a water content of Io to 28% and (b) from about 5 % to about 95% by weight of a water-soluble, organic, surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. That the aluminosilicate 2 * The composition of claim 1, characterized in that a particle diameter of about o, 2 microns to etv; _Oj has a y microns. 3- Composition according to claim 1, characterized in that the ratio of ζ to y in the general formula im Range from about l, o to etv; a ο, 8. 409848/1030 Ii ■■ 4-. Zu3o.mffien £? Etzuri £ after. Claim 5, characterized in that that the Aluruinosilicationonyastauschiamaterial die formula Na ₁₂ (Al0 ₂ .Si0 _{2) 12} .27 H ₃ O or Na ₈₆ / "(Al0 _{2) 86} (Si0 _{2) 106} _7264E ₂ 0 has. 5. Composition according to claim 1, characterized in that that they additionally have about 5 wt. -25 "to about 50.Gsvr.-50 a detergent builder salt. 6. Composition according to claim 5, characterized in that that the auxiliary builder consists of sodium pyrophosphate, sodium tripolyphosphate, sodium carbonate, I sodium bicarbonate, ITodium silicate, sodium citrate, sodium oxydisuccinate, Sodium mellitate, liatrium nitrilotriacetate, sodium ethylenediaminetetraacetate, Sodium polymaleate, liatrium polyitaconate, Sodium polymesaconate, ITodium polyfumarate, sodium polyaconitate, Natriuiapolycitraconat, Uatriuapolyiaethylenmalonat, Sodium Carboxymethyloxymalonat, ITatriuiacarboxyniethyloxysuccinat, Sodium cis -cyclohexane hexacarboxylate, cis -cyclopentane tetracarboxylate and Ifatriuiiiphloroglucin ^^ trisulxonate comprising Group is selected. 7- composition according to claim 6, characterized in that that it contains the auxiliary builder in an amount of about 10 Gev /.-% to about 35 Gev /.- ^. 8. Composition according to claim 7, characterized in that that they are used as auxiliary builder sodium pyrophosphate, sodium tripolyphosphate, ifodium nitrilotriacetate or sodium citrate contains. 9. Composition according to claim 8, characterized in that the weight ratio of the aluminosilicate ion exchange material to the pyrophosphate is in the range from about Λ : 2 to about 2: 1. - 47 - 409848/1030 10. Composition according to claim 8, characterized in that indicates that the weight ratio of the aluainosilicate ion exchange material zua synthetic builder from the Group sodium tripolyphosphate and hatriuianitrilotriacetate is in the range from about 1: 1 to about 1: 3- 11. Y / aschraittel composition, which for rapid.reduction the content of free, melmvertigem metal ion in an aqueous solution containing: (a) etv.'a 5 % to about 95% by weight of a water-insoluble inorganic aluminum ion exchange material of the formula wherein χ is an integer from about 20 to about 30, with a particle diameter of about 1 micron to about 100 microns, a calcium ion exchange capacity of at least about 200 mg-equivalent / g and one . Calcium ion exchange rate of at least about 0.129 g / ?, 8 l / min / g and '-' (b) about 5 wt -.% to about 95 wt -.% of a wasserlösIichen, organic detergent compound selected from the anionic, nonionic, and zwitterionic detergents and comprehensive ampholytischa mixtures thereof group - .12- Composition according to claim 11, characterized in that the aluminum inosilicate ion exchange material is a Has particle size from about 1 micron to about 10 microns. . 13. Composition according to claim 11, characterized in that the alurainosilicate ion exchange material is · (AlO ₂ -SiO ₂ ) ₁₂ -27 H ₂ O. ORIGINAL BATHROOM / 4098A8 / 1030 14. The composition of claim. 1.3, characterized in that the Aluminos ilic ati onenaus al tauschiaateri a particle diameter of about 1 micron Ms about 10 microns and a calcium ion exchange capacity of about 300 ing equivalently / e; up to about 352 mg-equivalent / g. 15. Composition according to claim 14, characterized in that that the aluminosilicate ion exchange material also a calcium ion exchange rate of at least about 0.26 g / 3.8 l / min / g. 16. The composition according to claim 11, characterized in that the detergent compound is a water-soluble The salt of an organic sulfuric acid reaction product that has an alkyl group with about 8 "to about 22 carbon atoms and a sulfonic acid or Contains sulfuric acid ester group. 17. Composition according to claim 11, characterized in that the detergent compound is water-soluble Soap is. 18. The composition according to claim 11, characterized in that the water-soluble organic detergent compound from the sodium-linear-C - ^ - CLo-alkylbenzenesulfonate; Triethanolamine G ^ QC ^ Q -alkylbenzenesulfonate; Sodium tallow alkyl sulfate; H sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with about 3 to about 10 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of a tallow fatty alcohol with about 11 moles of ethylene oxide; 3 ~ (IT, N-dimethyl-coconut alkylammonio) -2-hydroxypropane-1-sulfonate; 3- (N ₁ UT-bimethyl-! T-coconut alkylammonio) -propane-1-sulfonate; 6- (1T-dodecylbenzyl-M "ϊΓ-dimethylaamonio) -hexanoate; dodecyldimethylarainoxid; coconut alkyldimethylamine oxide; the water-soluble -_ 49 - ORIGINAL BATHROOM 409848 / 1D30 Sn "Sodium and potassium salts of higher fatty acids, the 8 to 24 Kohl.nstoffatouie contain and their mixtures comprehensive group is selected. - . 19- Composition according to claim 11, characterized in that the water-soluble organic detergent compound is a mixture of alkyl ether sulfate compounds containing about 0.05% by weight to 5% by weight of mixtures of C ^ p-II "compounds, about 55% by weight % to 70% by weight of mixtures of , * c compounds, about 25% by weight to 40% by weight of mixtures of G ^ f-. "-" compounds, etv / a 0.1% by weight .-% to 5 of mixtures of C _{/] 8} _- _l q- ^Ve rbindungen, about 1'5 Gevi .'-% to 25 wt .-% of mixtures of compounds having a Ä'thoxylierungsgrad of O ₁ about 50 percent by .- # to 65 wt -.% of mixtures of compounds having a degree of ethoxylation 1-4 ·, about 12 wt -.% to 22 wt -.% of mixtures of compounds having a degree of ethoxylation of 5 to 8 and about 0.5 Gew.-jS up to 10 wt .-% of mixtures of compounds with a degree of ethoxylation of more than 8 contain. .20- composition according to claim 11, characterized in that the water-soluble organic detergent compound is a mixture of a-01efinsulfonaten, consisting essentially of about 30 wt .-% to about 70 wt -.% Of a component A, about 20 parts by weight % to about 70 wt .-% of a component B and about 2 wt -.% to about 15 wt .-% of a component C consists wherein (a) component A is a mixture of double bond position isomers of water-soluble salts of alkene-1-sulfonic acids having about 10 to about 24 carbon atoms, the mixture of positional isomers etv / a 10 % to about 25% of an α, β-unsaturated isomer, contains about 30% to about 70 % of a β, γ-unsaturated isomer, about 5 % to about 25 % of a γ, cT-unsaturated isomer, and about 5% to about 10 % of a Cf ₁ ε-unsaturated isomer; 4098 * 48/1030 (To) component B is a mixture of water-soluble salts. Functionally substituted sulfur-containing saturated aliphatic compounds having from about 10 to about carbon atoms, the functional units being hydroxyl and "sulfonate groups" and the sulfonate groups always being on the terminal carbon atom, while the hydroxyl group is bonded to a carbon atom which is at least 2 carbon atoms away from the terminal ones Carbon atoms and at least 90 % of the hydroxyl group substituents are in the 3, 4 and 5 positions; and (c) component C is a mixture which is about 30 % to 95 % water-soluble salts of alkene disulfonates having about 10 to about 24 carbon atoms and about 5 % to about 70% water-soluble salts of hydroxydisulfonates and about 10 to about 24 carbon atoms, wherein the alkene disulfonates have one sulfonate group bonded to a terminal carbon atom and a second sulfonate group bonded to an inner carbon atom which is not more than about 6 carbon atoms away from the terminal carbon atom, the alkene double bond is between the terminal carbon atom and approximately the 7 carbon atom, The hydroxydisulfonates are saturated aliphatic compounds with a sulfonate group bonded to a terminal carbon atom, a second sulfonate group which is bonded to an ionic carbon atom more than about β carbon atoms from the terminal carbon atom, and a hydroxyl group which is carbon is bonded to a substance atom that is no more than about 4 carbon atoms away from the point of attachment of the "wide sulfonate group. BAD ORsGiNAL - 51 - 409848/1030 S3 21. The composition of claim. 11, characterized in that that they are about 5 Gev /.-$ as an additional component to .about 50% by weight of a water-soluble detergent auxiliary builder contains. 22. Composition according to claim 21, characterized in that that the auxiliary builder sodium nitride polyphosphate or potassium tripolyphosphate. · 23. Composition according to claim 21, characterized in that that the auxiliary builder is a phosphorus-free builder. 24. Composition according to claim 23, characterized in that that the auxiliary builder is a water-soluble inorganic carbonate, bicarbonate or silicate salt. 25 Composition according to Claim 23, characterized in that that the auxiliary builder from the water-soluble organic polyacetates, carboxylates, and polycarboxylates Polyhydroxysulfonate comprehensive group is selected. 26. The composition of claim 23, characterized in that the auxiliary builder sodium carbonate from the carbonate, sodium bicarbonate, Katriumslllcat, sodium citrate, Natriumoxydisuccinat, Natriummellithat, Natriumnltrllotriaeetat, disodium ethylenediaminetetraacetate, Natriurapolymaleafc, Ifatrluittpolyitaconat, Natriumpolymesaconat, Natriumpolyf umarat, Na triumpolyaconitat, ÜTatriumpolycitraconat, üfatriumpolyniethy-! · Lenmalonat , Sodium carboxymethylmalonate, sodium carboxyme - thyloxysuccinate, sodium cis-cyclohexane hexacarboxylate, cis-cyclopentane tetracarboxylate and sodium phloroglucine trisulfonate is selected - Y / ash composition, which for rapid reduction the content of free, polyvalent metal ions - 52 409848/1030 in an aqueous solution containing: (a) about 20 wt.% to ~ et ^T '? a 50 wt .- $ of a water-insoluble inorganic Aluminosilicationenaustausehmaterials of formula Na ^ ₂ (AlO ₂ -SiO ₂ ) ^ 2 ^{#x H} 2 ⁰ ' wherein χ is an integer from about 20 to about 30, with a particle diameter of from about 1 micron to
about 100 microns, a calcium ion exchange capacity of about 300 mg equivalent / g to about 352 mg equivalent / g, and a calcium ion exchange rate of at least about 0.26 g / 3.8 L / min / g; (b) about. . 15 weight -% to about 50 wt .-% of a water-soluble organic detergent compound selected from the anionic, nonionic, ampholytic and zwitterionisehe detergents and mixtures thereof the group comprising; (c) about 5% by weight to about 50% by weight of an auxiliary builder salt from the sodium tripolyphosphate, sodium carbonate, Sodium bicarbonate, sodium silicate, sodium citrate, Sodium oxydisuccinate, sodium mellitate »sodium nitrilotriacetate, Sodium ethylenediamine tetraacetate, sodium polymaleate, sodium polyitaconate, sodium polyniesaconate, Sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, Sodium polymethylene malonate, sodium carboxymethyloxymalonate, Sodium carboxymethyloxysuccinate, Sodium cis-cyclohexane hexacarboxylate »cis-cyclopentane tetracarboxylate and sodium phloroglucine trisulfonate comprehensive group and (d) about 5 wt -.% "to about 25 wt .- $ of a pH controlling agent, wherein the Pji of a 0,05 wt .-% aqueous solution of the composition in the range of about 9t5 to etv / a .10.2 lies. "- 53 - 4 0 9 8 4 8 / 1030- KusfiintisnuctKUng according to claim 27 »thereby keatagelehnet, öaß aas Alurairiaslii
.SiOp) ₁₂ .27 K ₂ O. is 29- composition; according to claim. 27 »thereby keiin-> draws that the ϊonexauscb.ssa.terlal one, ieilcliett.-diameter from about 1 micron to about 10 microns. 30- Y / water softening & e additives, containing: (a) about 5% to about 95% by weight of a water soluble inorganic alurainosilicate ion exchange materials the formula "" ■ v / orin x. is an integer from about 20 to about 30, with a particle diameter of about 1 micron to about. ^r a 100 microns, a calcium ion exchange capacity. of at least about 200 Eg-Iqulvalent / g and a calcium exchange rate of at least about 0.26 g / 3.8 l / min / g and (b) about 5 Qe \ r .-% to about 95 Gevs. ~% of an auxiliary builder. 31- additive according to claim 30, characterized in that the aluminosilicate material is (.27 K ₂ O). ₁₂ (AlO ₂ -SiO ₂ ) _{Λ 2} 32. Composition: after. Claim 30, characterized in that the auxiliary builder consists of "the water-soluble Phosphates, polyphosphates, carbonates, bicarbonates ", silicates, carboxylates, polycarbojcylates, polyhydroxysulfonates and their Mixtures comprehensive group is selected. . · ': BAD dR! Si - \! AL 4098A8 / 1030 33. Composition according to claim 30, which denotes gelee, that the auxiliary fuel from the ITatriuatripolyphos phat, sodium carbonate,. Sodium bicarbonate sodium silicate, FatriuEicitrate, ITatriusoxydisucciriat, Katriuminellithat, Fatrius mitrilotriacetat, ITatriuiaäthylendiaaiintetraacetat, UatriUTnpolyisale at, Natriumpolyi tac onat, ITatriunipolynies ac onat Sodium polyfumarate, sodium polyaconitate, ITodium polycitraconate j liatrium polyethylene malonate, sodium carboxyaethyloxymalonate, I sodium carboxyniethyloxysuccinate, I sodium cis-cyclohexane hexacarboxylate, cis -cyclopentane tetracarbylate and ITodium di-chloroglucine trisulfonate usif as send group selected is. Composition according to Claim 30, characterized in that da3 is the weight ratio of aluminosilicate to Builder is about 5: 1 to about 1: 5. For: The Procter & Gamble Company Cincinnati j Ohio, V.St.A. Dr. ^. Beil Lawyer ORIGINAL INSPECTED - 55 409848/10